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United States Patent |
5,608,002
|
Kubo
,   et al.
|
March 4, 1997
|
Water- and oil-repelling agent composition and process for preparing
the same
Abstract
Process for preparing a water- and oil-repelling agent composition, which
is obtained by solution-polymerizing a polymerizable monomer component
which contains at least a monomer having a polyfluoroalkyl group in a
polymerization solvent which contains at least one compound with a boiling
point of 0.degree. to 150.degree. C. selected from the group consisting of
a hydrochlorofluorocarbon having 2 to 3 carbon atoms and a
hydrofluorocarbon having 4 to 6 carbon atoms and 4 or more fluorine atoms,
said solvent containing the compound in an amount of at least 5% by
weight, and the water- and oil-repelling agent composition prepared
thereby.
Inventors:
|
Kubo; Motonobu (Settsu, JP);
Hayashi; Kazunori (Settsu, JP)
|
Assignee:
|
Daikin Industries, Ltd. (Osaka, JP)
|
Appl. No.:
|
464711 |
Filed:
|
July 21, 1995 |
PCT Filed:
|
October 21, 1994
|
PCT NO:
|
PCT/JP94/01778
|
371 Date:
|
July 21, 1995
|
102(e) Date:
|
July 21, 1995
|
PCT PUB.NO.:
|
WO95/11949 |
PCT PUB. Date:
|
May 4, 1995 |
Foreign Application Priority Data
Current U.S. Class: |
524/795; 524/462; 526/206; 526/242; 526/243; 526/245; 526/246; 526/247; 526/248; 526/250; 526/251; 526/253; 526/254; 526/255 |
Intern'l Class: |
C08K 005/02; C08F 016/24; C08F 014/18; C08F 012/20 |
Field of Search: |
524/795,462
526/206,242,245,247,248,251,243,246,250,253,254
|
References Cited
U.S. Patent Documents
3919183 | Jan., 1975 | Jager et al. | 526/245.
|
5182342 | Jan., 1993 | Feiring et al. | 526/206.
|
5494984 | Feb., 1996 | Funaki et al. | 526/255.
|
Foreign Patent Documents |
3-17106 | Jan., 1991 | JP.
| |
6-157612 | Jun., 1994 | JP.
| |
6-157614 | Jun., 1994 | JP.
| |
6-157616 | Jun., 1994 | JP.
| |
6-157617 | Jun., 1994 | JP.
| |
6-157613 | Jun., 1994 | JP.
| |
Other References
International Search Report for International Appln. No. PCT/JP94/01778.
|
Primary Examiner: Szekely; Peter A.
Attorney, Agent or Firm: Varndell Legal Group
Claims
We claim:
1. A process for preparing a water- and oil-repelling agent composition,
which comprises solution-polymerizing a polymerizable monomer component
which contains at least a monomer having a polyfluoroalkyl group in a
polymerizing solvent which contains at least one compound (A) selected
from the group consisting of
1,1-dichloro-1-fluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane,
1,3-dichloro-1,1,2,2,3-pentafluoropropane,
1,1,1,2,2-pentafluorobutane,
1,1,1,2,3,3,4-heptafluorobutane,
1,1,1,2,3,4,4-heptafluorobutane,
1,1,2,2,3,4,4-heptafluorobutane,
1,2,3,3,4,4-hexafluorocyclobutane,
2-trifluoromethyl-1,1,1,2,4,4-hexafluoropentane,
1,1,1,2,2,5,5,5-octafluoropentane,
2-trifluoromethyl-1,1,1,2,3,3,4,4-octafluoropentane,
2-trifluoromethyl-1,1,1,4,4,5,5,5-octafluorohexane,
2-trifluoromethyl-1,1,1,2,3,4,5,5,5,-nonafluorohexane and
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluorohexane,
said solvent containing the compound (A) in an amount of at least 5% by
weight.
2. The process for preparing the water- and oil-repelling agent composition
of claim 1, wherein the compound (A) is at least one member selected from
the group consisting of 1,1-dichloro-1-fluoroethane and
1,2,3,3,4,4-hexafluorocyclobutane.
3. The process for preparing the water- and oil-repelling agent composition
of claim 1, wherein the polymerization solvent contains
1,1-dichloro-1-fluoroethane in an amount of at least 10% by weight.
4. The process for preparing the water- and oil-repelling agent composition
of claim 1, wherein the compound (A) contains both a fluorine atom and a
chlorine atom and is other than trichlorotrifluoroethane and
1,1,1-trifluoroethane.
5. The process for preparing the water- and oil-repelling agent composition
of claim 1, wherein the compound (A) is at least one member selected from
the group consisting of
1,1-dichloro-1-fluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane,
1,3-dichloro-1,1,2,2,3-pentafluoropropane,
1,1,1,2,2-pentafluorobutane,
1,1,1,2,3,3,4-heptafluorobutane,
1. 1,1,2,3,4,4-heptafluorobutane,
1,1,2,2,3,4,4-heptafluorobutane,
1,2,3,3,4,4-hexafluorocyclobutane,
2-trifluoromethyl-1,1,1,2,4,4-hexafluoropentane,
2-trifluoromethyl-1,1,1,2,3,3,4,4-octafluoropentane,
2-trifluoromethyl-1,1,1,4,4,5,5,5-octafluorohexane,
2-trifluoromethyl-1,1,1,2,3,4,5,5,5,-nonafluorohexane, and
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluorohexane.
6. A water- and oil-repelling agent composition, which is obtained by
solution-polymerizing a polymerizable monomer component which contains at
least a monomer having a polyfluoroalkyl group in a polymerizing solvent
which contains at least one compound (A) selected from the group
consisting of
1,1-dichloro-1-fluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane,
1,3-dichloro-1,1,2,2,3-pentafluoropropane,
1,1,1,2,2-pentafluorobutane,
1,1,1,2,3,3,4-heptafluorobutane,
1,1,1,2,3,4,4-heptafluorobutane,
1,1,2,2,3,4,4-heptafluorobutane,
1,2,3,3,4,4-hexafluorocyclobutane,
2-trifluoromethyl-1,1,1,2,4,4-hexafluoropentane,
1,1,1,2,2,5,5,5-octafluoropentane,
2-trifluoromethyl-1,1,1,2,3,3,4,4-octafluoropentane,
2-trifluoromethyl-1,1,1,4,4,5,5,5-octafluorohexane,
2-trifluoromethyl-1,1,1,2,3,4,5,5,5,-nonafluorohexane, and
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluorohexane,
said solvent containing the compound (A) in an amount of at least 5% by
weight.
7. The water- and oil-repelling agent composition of claim 6, wherein the
compound (A) is at least one member selected from the group consisting of
1,1-dichloro-1-fluoroethane and 1,2,3,3,4,4-hexafluorocyclobutane.
8. The water- and oil-repelling agent composition of claim 6, wherein the
polymerization solvent contains 1,1-dichloro-1-fluoroethane in an amount
of at least 10% by weight.
9. The water- and oil-repelling agent composition of claim 6, wherein the
compound (A) contains both a fluorine atom and a chlorine atom and is
other than trichlorotrifluoroethane and 1,1,1-trifluoroethane.
10. The water- and oil-repelling agent composition of claim 6, wherein the
compound (A) is at least one member selected from the group consisting of
1,1-dichloro-1-fluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane,
1,3-dichloro-1,1,2,2,3-pentafluoropropane,
1. 1,1,2,2-pentafluorobutane,
1,1,1,2,3,3,4-heptafluorobutane,
1,1,1,2,3,4,4-heptafluorobutane,
1,1,2,2,3,4,4-heptafluorobutane,
1,2,3,3,4,4-hexafluorocyclobutane,
2-trifluoromethyl-1,1,1,2,4,4-hexafluoropentane,
2-trifluoromethyl-1,1,1,2,3,3,4,4-octafluoropentane,
2-trifluoromethyl-1,1,1,4,4,5,5,5-octafluorohexane,
2-trifluoromethyl-1,1,1,2,3,4,5,5,5,-nonafluorohexane, and
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluorohexane.
11. A water- and oil-repelling agent composition which is obtained by
solution-polymerizing a polymerizable monomer component which contains at
least a monomer havening a polyfluoroalkyl group in the absence of
trichlorotrifluoroethane and/or 1,1,1-trifluoroethane but in the presence
of a polymerizing solvent which contains at least one compound (A) with a
boiling point of 0.degree. to 150.degree. C. selected from the group
consisting of a hydrochlorofluorocarbon having 2 to 3 carbon atoms and a
hydrofluorocarbon having 4 to 6 carbon atoms and 4 or more fluorine atoms,
said solvent containing the compound (A) in an amount of at least 5% by
weight.
12. The water- and oil-repelling agent composition of claim 11, where the
monomer component is a mixture of a monomer having a polyfluoroalkyl group
and a monomer free of polyfluoroalkyl group at a weight ratio of 20/80 to
100/0, and the monomer component is used in the amount of 0.5 to 50% by
weight on the basis of the total weight of the monomer component and the
polymerization solvent.
13. The water- and oil-repelling agent composition of claim 11, wherein the
monomer having a polyfluoroalkyl group is a polyfluoroalkyl
group-containing (meth)acrylic acid ester.
14. The process for preparing the water- and oil-repelling agent
composition of claim 11, wherein the compound (A) contains both a fluorine
atom and a chlorine atom.
15. A process for preparing a water- and oil-repelling agent composition,
which comprises solution-polymerizing a polymerizable monomer component
which contains at least a monomer havening a polyfluoroalkyl group in a
polymerizing solvent which contains at least one compound (A) with a
boiling point of 0.degree. to 150.degree. C. selected from the group
consisting of a hydrochlorofluorocarbon having 2 to 3 carbon atoms and a
hydrofluorocarbon having 4 to 6 carbon atoms and 4 or more fluorine atoms,
said solvent containing the compound (A) in an amount of at least 5% by
weight.
16. The process for preparing the water- and oil-repelling agent
composition of claim 15, where the monomer component is a mixture of a
monomer having a polyfluoroalkyl group and a monomer free of
polyfluoroalkyl group at a weight of 20/80 to 100/0, and the monomer
component is used in an amount of 0.5 to 50% by weight on the basis of the
total weight of the monomer component and the polymerization solvent.
17. The process for preparing the water- and oil-repelling agent
composition of claim 15, wherein the monomer having a polyfluoroalkyl
group is a polyfluoroalkyl group-containing (meth)acrylic acid ester.
18. The process for preparing the water- and oil-repelling agent
composition of claim 15, wherein the compound (A) contains both a fluorine
atom and a chlorine atom and is other than trichlorotrifluoroethane and
1,1,1-trifluoroethane.
Description
TECHNICAL FIELD
The present invention relates to a fluorine-containing water- and
oil-repelling agent composition and particularly relates to a
solution-polymerization type water- and oil-repelling agent composition
prepared by polymerizing or copolymerizing a monomer having a
polyfluoroalkyl group in a specific fluorine-containing solvent, and a
process for the preparation.
BACKGROUND ART
As a water- and oil-repelling agent composition to be used for dry cleaning
of clothes and for water-proof spray, there has been heitherto used a
solution-polymerization type water- and oil-repelling agent composition
using a trichlorotrifluoroethane (CFC113) and/or 1,1,1-trichloroethane as
a polymerization solvent from the viewpoint of water- and oil-repelling
effect and easiness in handling thereof (JP-B-64635/1992 and
JP-B-65113/1992).
However, it was recently decided in a worldwide scale to prohibit the
production of such solvents as trichlorotrifluoroethane and
1,1,1-trichloroethane for the purpose of protection of the ozone layer,
and it is urgently needed to find out a solvent replacing these toxic ones
for the water- and oil-repelling agent composition.
As alternative solvents, hydrocarbons, perchloroethane, esters, ketones and
the like have being studied (JP-A-78425/1993), and in these solvents a
perfluoroalkyl group-containing monomer and a monomer free of fluorine
atom are copolymerized. However, usually if a mixing ratio of the monomer
having a perfluloroalkyl group is increased, though water- and
oil-repelling property is enhanced, there is a tendency that precipitate
is formed and storage stability becomes worse. If a mixing ratio of the
monomer free of fluorine atom is increased, though stability is improved,
the water- and oil-repelling property tends to be worse, and it is
difficult to obtain a practical composition.
The present invention was made in consideration of the above-mentioned
problems, and it is an object to provide a water- and oil-repelling agent
composition which is excellent in storage stability and water- and
oil-repelling property, and serves to remarkably decrease or completely
avoid the destruction of the ozone layer, and a process for preparation
thereof.
DISCLOSURE OF THE INVENTION
The above-mentioned object can be accomplished by solution-polymerizing a
polymerizable monomer component containing at least a polyfluoroalkyl
group-containing monomer in a polymerization solvent containing at least
5% (% by weight, hereinafter the same) of at least one kind of compound
selected from a group consisting of a hydrochloroflurocarbon being called
an alternative Freon and having 2 to 3 carbon atoms and a
hydrofluorocarbon having 4 to 6 carbon atoms and 4 or more fluorine atoms.
PREFERRED EMBODIMENTS OF THE INVENTION
One of the features of the present invention is to use a specific
fluorine-containing polymerization solvent.
It is preferred that the polymerization solvent to be used in the present
invention has a boiling point of 0.degree. to 150.degree. C., especially
20.degree. to 100.degree. C., further especially 30.degree. to 80.degree.
C. If the boiling point is lower than 0.degree. C., handling of products
tends to become difficult, and if it is higher than 150.degree. C., drying
of the treated article becomes slow and there is a tendency of causing
problem in viewpoint of operability.
As the hydrochloroflurocarbon to be used in the present invention and
having a boiling point of 0.degree. to 150.degree. C. and 2 to 3 carbon
atoms, there are a dichlorofluoroethane such as
1,1-dichloro-1-fluoroethane (HCFC141b) (boiling point: 32.degree. C. ), a
dichloropentafluoropropane such as
1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC225ca) (boiling point:
51.degree. C.), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC225cb)
(boiling point: 54.degree. C.), and the like.
Also, as the hydrofluorocarbon having a boiling point of 0.degree. to
150.degree. C., 4 to 6 carbon atoms and 4 or more fluorine atoms, there
are hydrofluorocarbons of a butane type, a cyclobutane type, a pentane
type and a hexane type. As the butane type hydrofluorocarbon, there are a
pentafluorobutane such as 1,1,1,2,2-pentafluorobutane (boiling point:
40.degree. C.), a heptafluorobutane such as
1,1,1,2,3,3,4-heptafluorobutane (boiling point: 42.degree. C.),
1,1,1,2,3,4,4-heptafluorobutane (boiling point 48.degree. C.) or
1,1,2,2,3,4,4-heptafluorobutane (boiling point: 57.degree. C.), an
octafluorobutane such as 1,1,2,2,3,3,4,4-octafluorobutane (boiling point:
44.degree. C.). As the cyclobutane type hydrofluorocarbon, there are
1,1,2,2-tetrafluorocyclobutane (boiling point 50.degree. C.),
1,2,3,3,4,4-hexafluorocyclobutane (boiling point: 63.degree. C.), and the
like. As the pentane type hydrofluorocarbon, there are a hexafluoropentane
such as 2-trifluoromethyl-1,1,1,2,4,4-hexafluoropentane (boiling point:
46.degree. C.), an octafluoropentane such as
1,1,1,2,2,5,5,5-octafluoropentane (boiling point: 49.degree. C.) or
2-trifluoromethyl-1,1,1,2,3,3,4,4-octafluoropentane (boiling point:
55.degree. C.), a decafluoropentane such as
1,1,1,2,2,3,4,5,5,5-decafluoropentane (boiling point: 55.degree. C.), and
the like. As the hexane type hydrofluorocarbon, there are an
octafluorohexane such as
2-trifluoromethyl-1,1,1,4,4,5,5,5,-octafluorohexane (boiling point:
57.degree. C.), a fluorohexane such as
2-trifluoromethyl-1,1,1,2,3,4,5,5,5-nonafluorohexane (boiling point:
65.degree. C.), a decafluorohexane such as
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluorohexane (boiling point:
62.degree. C.), and the like. The hydrofluorocarbon having not more than 3
carbon atoms has a low boiling point, and is difficult to handle and
disadvantageous in production cost.
Among them, as the hydrochlorofluorocarbon, 1,1-dichloro-1-fluoroethane is
particularly preferable, and as the hydrofluorocarbon,
1,1,2,3,3,4,4-octafluorobutane, 1,2,3,3,4,4-hexafluorocyclobutane and
1,1,1,2,2,3,4,5,5,5 -decafluoropentane are particularly preferable. These
may be used alone or in combination of two or more kinds thereof.
The polymerization solvent comprises at least 5%, preferably not less than
10%, more preferably not less than 20% (preferable upper limit being 100%)
of at least one compound selected from the group consisting of the
above-mentioned hydrochloroflurocarbon and the hydrofluorocarbon. When
less than 5%, there is a tendency that the desired object to keep a better
storage stability with maintaining a water- and oil-repelling property
cannot be accomplished. Particularly in case where the polymerization
solvent contains 1,1-dichloro-1-fluoroethane, 1,1-dichloro-1-fluoroethane
is preferably contained in a ratio of at least 10%, particularly not less
than 20%, more particularly not less than 25% (preferable upper limit
being 100%). When less than 10%, there is a tendency that a storage
stability and foaming property are lowered in case where the mixing ratio
of the polyfluoroalkyl group-containing monomer is increased.
The polymerization solvent may contain a co-solvent in addition to the
above-mentioned hydrochloroflurocarbon and hydrofluorocarbon.
As the co-solvent, there are used a petroleum solvent such as n-hexane,
n-decane or gasoline for industrial use, a chlorine-containing solvent
such as perchloroethylene or trichloroethylene, an ester such as ethyl
acetate or butyl acetate, a ketone such as acetone or methyl ethyl ketone,
a glycol(ether) such as ethylene glycol, propylene glycol or propylene
glycol monomethyl ether, and the like.
It is preferable that the co-solvent content in the polymerization solvent
is not more than 95%, particularly not more than 90%, more particularly
not more than 80%. When more than 95%, there is a tendency that a
necessary amount of at least one kind selected from the group consisting
of the above-mentioned hydrochlorofluorocarbon and hydrofluorocarbon
cannot be used and the water- and oil-repelling agent composition being
excellent in water- and oil-repelling property cannot be obtained.
The monomer component to be solution-polymerized in the polymerization
solvent comprises at least a polyfluoroalkyl group-containing monomer.
As the polyfluoroalkyl group-containing monomer, there is a polyfluoroalkyl
group-containing (meth)acrylic acid ester represented by
##STR1##
(R.sub.1 is H or CH.sub.3, Rf is defined hereinafter). Examples are, for
instance, perfluorooctylethyl acrylate, 2-perfluorooctyl-1-methylethyl
acrylate, 2-(N-ethylperfluorooctasulfoamide)ethyl acrylate and the like.
Also, as a suitable monomer, there is a vinyl compound represented by
##STR2##
(R.sub.1 is as defined above, Rf is defined hereinafter). Examples are
perfluorooctylethylene, perfluorooctyloxyphenylethylene and the like. It
is possible to use in combination of two or more kinds thereof.
The above-mentioned Rf is a linear or branched polyfluoroalkyl group having
3 to 21 carbon atoms, preferably 4 to 16 carbon atoms. Usually a group
having a perfluoroalkyl group at its end is selected, but a group having
hydrogen atom or chlorine atom or a group containing oxypolyfluoroalkylene
may be employed.
As the monomer component, there may be used a monomer free of a
polyfluoroalkyl group in addition to the above-mentioned polyfluoroalkyl
group-containing monomer. It is preferable that a weight ratio of the
polyfluoroalkyl group-containing monomer to the monomer free of
polyfluoroalkyl group is 20/80 to 100/0, particularly 30/70 to 100/0. If
this weight ratio is less than 20/80, there is a tendency that a better
water-repelling property cannot be obtained.
As the monomer free of polyfluoroalkyl group, there may be used a compound
having a radical reactive unsaturated bond, for example, a methacrylic
acid and an acrylic acid or an ester thereof represented by
##STR3##
(R.sub.1 is as defined above, R.sub.2 is H or C.sub.p H.sub.2p+1 (p is an
integer of 1 to 23 ), q is an integer of 1 to 30), for example, stearyl
(meth )acrylate, 2-ethylhexyl (meth)acrylate, lauryl acrylate,
polyethylene glycol mono (meth)acrylate, glycidyl (meth)acrylate,
polyethylene glycol di(meth)acrylate, and the like. Also there may be used
monomers represented by
##STR4##
(R.sub.1 is as defined above), for example, ethylene, vinyl alkyl ether,
maleic acid anhydride, styrene, .alpha.-methylstyrene, p-methylstyrene,
acrylonitrile, butadiene, isoprene, chloroprene, methyl vinyl ketone and
the like, in addition to a (meth)acrylic amide derivative, a
halogen-containing vinyl monomer such as vinyl chloride or vinylidene
chloride, vinyl acetate, maleic acid dialkyl ester, vinyl alcohol, and the
like.
It is preferable that an amount of the monomer component is 0.5 to 50%,
particularly 1.0 to 50%, more particularly 5 to 45% on the basis of a
total weight of the monomer component and the polymerization solvent. When
less than 0.5%, there is a tendency that, a yield of polymer per unit
polymerization lowers, resulting in an economical disadvantage. When more
than 50%, there is a tendency that gelation of a polymerization system are
liable to occur and the reaction becomes difficult to continue.
The solution is polymerization is preferably conducted in a pressure
resistive reaction vessel like an autoclave, if necessary, at a
temperature of 20.degree. to 200.degree. C., particularly 30.degree. to
150.degree. C., more particularly 40.degree. to 130.degree. C. usually by
adding a polymerization initiator. When the polymerization temperature
becomes lower than 20.degree. C., the unreacted monomer tends to remain.
When it becomes higher than 200.degree. C., the inner pressure of the
autoclave rises too high and the production tends to become difficult from
a mechanical viewpoint. The reaction time depends on the reaction
temperature, and is usually from about 1 to hours, preferably about 2 to
about 15 hours, more preferably about 3 to about 10 hours.
As the polymerization initiator, there is used an organic peroxide, an azo
compound including an azobis compound, a persulfate and the like, and may
be employed an ionizing radiation such as .gamma. rays.
For example, when a vinyl compound is used as the monomer component, the
solution polymerization can be conducted by a known method applicable to
polymerization of vinyl compounds. The polymerization can be carried out
in a vessel equipped with an stirrer and means for external heating or
cooling. More particularly, the polymerization is carried out, for
example, in the following manner. First, the monomer component is added to
the polymerization solvent, and the polymerization is conducted in the
presence of the polymerization initiator with the content of the monomer
components being from 0.5 to 50% on the basis of the total weight of the
monomer component and the polymerization solvent, and the temperature of
the solution comprising the monomer component and the polymerization
solvent being from 40.degree. to 150.degree. C. The polymerization
initiator, when the vinyl compound is used as the monomer component, may
be any of known chemicals for initiating solution polymerization of an
unsaturated vinyl compound. Usually an azo compound and a peroxide soluble
in the solvent are used. As the peroxide, there are an acyl peroxide such
as benzoyl peroxide or lauroyl peroxide, an organic perester such as
t-butyl perbenzoate and a dialkyl peroxide such as di-t-butyl peroxide. As
the azo compound, there are azobis (isobutylonitril) and azobis
(2,4-dimethylnitrile), and the like. An amount of the polymerization
initiator is usually 0.1 to 2% on the basis of the weight of the monomer
component.
There is a case where a molecular weight of the polymer can be controlled
by the polymerization initiator alone or by the other conditions. When the
control is insufficient only with them, a small amount of a chain transfer
agent such as an alkane (C1 to C12) thiol may be added.
It is preferable that a number-average molecular weight of the obtained
polymer is from 1,000 to 100,000, particularly from 5,000 to 70,000, more
particularly from 10,000 to 50,000. When the molecular weight is lower
than 1,000, water- and oil-repelling property tends to be lowered, and
when higher than 100,000, whitening and powdering tend to occur.
After the polymerization of the monomer component, there may be optionally
added a solvent other than the above-mentioned hydrochlorofluorocarbon and
hydrofluorocarbon, if necessary, in the water- and oil-repelling agent
composition of the present invention. It is one of the features of the
present invention that there occurs no problem with a water- and
oil-repelling property, dissolution stability, low temperature storage
stablity and the like, even if another solvent is added in the manner
mentioned above after the completion of the polymerization.
Despite that the solvent such as trichlorotrifluoroethane or
1,1,1-trichloroethane is not used as the polymerization solvent for the
water- and oil-repelling agent composition of the present invention, an
excellent water- and oil-repelling property can be obtained without
forming sediments and lowering a storage property, even when the mixing
ratio of the polyfluoroalkyl group-containing monomer is increased.
Thus the water- and oil-repelling agent composition of the present
invention comprises the polmerization product of the monomer component
containing the above-mentioned polyfluoroalkyl group-containing monomer,
and the above-mentioned polymerization solvent, if necessary, another
solvent, and an antistatic agent and a mildew proof agent as occasion
demands.
In addition, there is one feature of the present invention such that when
the composition is applied to a dry cleaning machine, there occurs only
little foaming of a dry cleaning solvent and thus reducing troubles caused
from foaming.
The water- and oil-repelling agent composition of the present invention can
be applied to a water- and oil-repelling agent for wood, metal and plastic
surface, a mold releasing agent, a liquid resin antisticking agent for
condensor lead wires and the like in addition to the use for dry cleaning.
The water- and oil-repelling agent composition of the present invention can
be used in the form of aerosol by adding, for example, a propellant. As
the propellant, there is preferably used a fluoroalkane or
chlorofluoroalkane having 1 or 2 carbon atoms, LPG gas or carbon dioxide.
Typical examples of the fluoroalkane or chlorofluoroalkane having 1 or 2
carbon atoms, there are dichlorotrifluoromethane,
trichlorotrifluoromethane, chlorodifluoromethane, chlorodifluoroethane,
dichloritrifluoroethane, tetrafluoroethane and a mixture of two or more
kinds thereof. Dichlorodifluoromethane is particularly preferable. It is
preferable that an amount of the propellant is from 0.05 to 2 times larger
than total weight of the polymer and polymerization solvent.
The present invention is specifically explained by means of Examples, but
the present invention is not limited to those Examples. In the Examples,
parts means parts by weight.
EXAMPLE 1
Experimental Example 1-1
An autoclave of stainless steel with a stirrer and a heater was charged
with, as the monomer component, 70 parts of perfluorooctylethyl acrylate
and 30 parts of stearyl acrylate, and as the polymerization solvent, 500
arts of 1,1-dichloro-1-fluoroethane (HCFC141b), and as the polymerization
initiator, 1 part of t-butyl peroxypivalate. The mixture was reacted at
70.degree. C. for 10 hours in nitrogen atmosphere with stirring, and then
the reaction was terminated by cooling to 20.degree. C. to obtain a water-
and oil-repelling agent composition.
Experimental Example 1-2
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 70 parts of perfluorooctylethyl acrylate and 30 parts of 2-ethylhexyl
acrylate as the monomer component.
Experimental Example 1-3
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 70 parts of perfluorooctylethyl acrylate and 30 parts of lauryl
acrylate as the monomer component.
Experimental Example 1-4
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 250 parts of HCFC141b and 250 parts of n-decane as the polymerization
solvent.
Experimental Example 1-5
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 500 parts of 1,1-dichloro-2,2,3,3,3-pentafluoropropane as the
polymerization solvent.
Experimental Example 1-6
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 500 parts of 1,1,2,2,3,3,4,4-octafluorobutane as the polymerization
solvent.
Experimental Example 1-7
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as Experimental Example 1-1 excepting the use of
500 parts of n-hexane as the polymerization solvent.
Experimental Example 1-8
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as Experimental Example 1-1 excepting the use of
500 parts of n-hexane as the polymerization solvent, and 10 parts of
perfluorooctylethyl acrylate and 90 parts of stearyl acrylate as the
monomer component.
Experimental Example 1-9
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 500 parts of toluene as the polymerization solvent.
Experimental Example 1-10
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 exceptling the use
of 500 parts of toluene as the polymerization solvent, and 70 parts of
perfluorooctylethyl acrylate and 30 parts of stearyl acrylate as the
monomer component.
Experimental Example 1-11
A water- and oil-repelling agent composition was prepared in the same
polymerization reaction as in Experimental Example 1-1 excepting the use
of 500 parts of trichlorotrifluoroethane as the polymerization solvent.
EXAMPLE 2
Experimental Example 2-1
The water- and oil-repelling agent composition prepared in Experimental
Example 1-1 was evaluated in views of the following items. The results and
kind of solvent used are shown in Table 1.
[Appearance after polymerization]
Appearance at 25.degree. C. is observed with naked eyes.
[Appearance after keeping at 0.degree. C.]
Appearance at 0.degree. C. is observed with naked eyes.
[Foaming property on diluting with n-decane]
The prepared water- and oil-repelling agent composition was diluted with 20
times larger amount of n-decane, and 100 ml thereof was transferred into a
500 ml graduated measuring cylinder and then sealed. A height (cm) of foam
from the liquid surface formed just after sufficiently shaking was
measured. The height of foam is preferably lower than 10 cm, because the
resulting heights in Experimental Examples 1-7 to 1-10 are 12 to 15 cm.
[Water-repelling property]
The prepared water- and oil-repelling agent composition was diluted with a
n-decane so that the solid content was 1%. After immersing a cotton fabric
and a nylon fabric to the diluted solution, the cotton fabric and the
nylon fabric were dried for 12 hours at room temperature. After that,
evaluation was conducted according to the showering method defined in
JIS-L-1092. The results are indicated as index when the state where water
is completely repelled is assumed to be 100. It is preferred that the
index is not less than 80.
[Oil-repelling property]
The prepared water- and oil-repelling agent composition was diluted with
n-decane so that the solid content was 1%. After immersing a cotton fabric
and a nylon fabric to the diluted solution, the cotton fabric and the
nylon fabric were dried for 12 hours at room temperature. After that,
evaluation was conducted according to the method defined in AATCC-118. The
results are indicated as integer of 0 to 8 when the state where water is
completely repelled is assumed to be 8. It is preferred that the result is
not less than 3, particularly not less than 4.
[Molecular weight of polymer]
Number-average molecular weight of the polymer is measured by GPC
(polystyrene standard).
Experimental Examples 2-2 to 2-11
The same evaluations as in Experimental Example 2-1 were carried out by
using the water- and oil-repelling agent compositions prepared in
Experimental Examples 1-2 to 1-11. The results and kind of polymerization
solvent used are shown in Table 1.
TABLE 1
__________________________________________________________________________
Foaming
property
Water-
Oil- MW or
Experi- Appearance
Appearance
on diluting
repelling
repelling
polymer
mental
Polymerization
Boiling point
after after keeping
with n-decane
property
property
(Number
Ex. No.
solvent (.degree.C.)
polymerization
at 0.degree. C.
(cm) C.sup.1)
N.sup.2)
C N average)
__________________________________________________________________________
2-1 Dichlorofluoro-
32 Homogeneous
Homogeneous
2 100
100
6 6 26000
ethane and clear
and clear
2-2 Dichlorofluoro-
32 Homogeneous
Homogeneous
2 100
100
6 6 30000
ethane and clear
and clear
2-3 Dichlorofluoro-
32 Homogeneous
Homogeneous
2 100
100
5 5 28000
ethane and clear
and clear
2-4 Dichlorofluoro-
Dichloro-
Homogeneous
Homogeneous
5 100
100
6 6 32000
ethan/n-Decane
fluoroethane = 32
and clear
and clear
(1/1) n-Decane = 174
2-5 1,1-Dichloro-
51 Homogeneous
Homogeneous
3 90 90 4 4 27000
2,2,3,3,3-penta- and clear
and clear
fluoropropane
2-6 1,1,2,2,3,3,4,4-
44 Homogeneous
Homogeneous
2 100
100
5 6 29000
Octafluorobutane and clear
and clear
2-7 n-Hexane 69 Partial Coagulation
15 70 80 3 4 27000
precipitation
of whole
of polymer
liquid
2-8 n-Hexane 69 Homogeneous
Homogeneous
12 50 50 0 0 26000
and clear
and clear
2-9 Toluene 111 Partial Precipitation
13 90 100
5 5 26000
precipitation
and separa-
of polymer
tion of
polymer
2-10 Toluene 111 Homogeneous
Coagulation
15 80 90 3 4 29000
and clear
of whole
liquid
2-11 Trichlorotri-
48 Homogeneous
Homogeneous
3 100
100
5 6 29000
fluoroethane and clear
and clear
__________________________________________________________________________
As is clear from Table 1, as to Experimental Examples 2-1 to 2-6 both the
water-repelling property and oil-repelling property are excellent, and the
foaming is little, and the storage stability is also excellent. As to
Experimental Examples 2-7, 2-9 and 2-10, the storage stability is worse,
and as to Experimental Example 2-8 though the storage stability is good,
all of the water-repelling property, oil-repelling property and foaming
property are worse. As to Experimental Example 2-11, the water-repelling
property, oil-repelling property, foaming property and storage stability
are excellent, but the used solvent is not legally usable.
INDUSTRIAL APPLICABILITY
The water- and oil-repelling agent composition of the present invention is
excellent in storage stability and water- and oil-repelling property, and
has a low foaming property, and thus troubles caused when applying to a
dry cleaning machine can be avoided. Further since solvents which has been
decided not to be produced such as trichlorotrifluoroethane and
1,1,1-trichloroethane are not used, the problem to degarde the ozone layer
cannot be occured.
The particular fluorine-containing polymerization solvent used in the
present invention can dissolve a polymer well and has a proper boiling
point, and thus is easily handled.
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